DOI: https://doi.org/10.15368/theses.2013.230
Available at: https://digitalcommons.calpoly.edu/theses/1151
Date of Award
12-2013
Degree Name
MS in Polymers and Coatings
Department/Program
Chemistry & Biochemistry
Advisor
Raymond Fernando
Abstract
This project consists of two parts. One area of focus in the first part is understanding the interactions between a non-ionic, block copolymer type dispersant and hydrophobically-modified, ethoxylated urethane (HEUR) associative thickeners in water. The dispersant was mixed at various concentrations (0-2% by weight) with HEUR thickeners at 1% by weight concentration in the aqueous medium. This study is an integral part of our attempts to determine mechanisms of viscosity drop when colorant dispersions are added to latex tint base formulations thickened with associative thickeners. One of the HEUR thickeners is a product that has been available for over three decades (HEUR RM-825), whereas the other, HEUR RM-995 is a product recently introduced to minimize the tint base viscosity drop. The old HEUR showed a definitive viscosity maximum as a function of the dispersant concentration. However, the new generation product did not indicate a viscosity maximum within the dispersant concentration range studied; instead it showed a small, but linear increase in viscosity as dispersant level was increased.
The next area of focus was on understanding the phase behavior, rheology, and interactions between polymer latex particles and a hydrophobically-modified, ethoxylated urethane (HEUR) associative thickener in water. The influence of the addition of surfactant in some of the systems was also studied. Several types of dispersions were made using two types of polymer latex, two associative thickeners, and two surfactants. Mixtures containing a small particle size acrylic latex and HEUR RM-825 exhibited the most interesting and complex phase behavior and rheology. In experiments wherein the latex particle volume fraction was kept constant, the addition of HEUR caused stable, followed by phase separated (syneresis) and stable mixtures as HEUR concentration was increased. The observed phase behavior is consistent with previous work reported by other investigators. However, detailed rheological data on systems such as these have not been reported, and this report presents the rheological data and correlate rheology with the phase behavior. The stable latex-HEUR mixtures at low HEUR levels show shear-thinning viscosity with well-defined low-shear Newtonian plateaus. As HEUR level is increased wherein syneresis is observed, erratic rheological profiles with shear-thickening are observed. When HEUR level is increased to a region where no syneresis is observed, low shear Newtonian plateaus re-appeared albeit at higher viscosities. The effects of added non-ionic and anionic surfactants on the dispersion are also studied.
The main focus of the second part of this project is hybrid organic-inorganic photovoltaics. They have been the focus of recent studies due to their promising use in low-cost, flexible electronics, which can be processed from solution by printing and coating techniques. Understanding the rheology of these nanocomposites is essential in controlling shear flows during printing and application processes. Through rheology, we can determine different properties of poly(3-hexylthiophene) and dodecanethiol (DDT) modified zinc oxide (ZnO-DDT). Semiconductor nanowires such as ZnO have rigid or rod-like macromolecule geometry. Therefore, they have a tendency to have a lytropic liquid crystal (LLC) phase. LLC orders occur spontaneously in solutions with rod-shaped or anistropic objects from isotropic phase to nematic phase above a critical volume fraction which was studied using ZnO-DDT. The shear-induced alignment of the liquid crystal molecules was analyzed, serving as a guide for LLC printing. Furthermore by using this nanocomposite we are able to induced gelation using the ZnO-DDT nanowires in what is considered as a “good solvent,” dichlorobenzene. The kinetics of this gelation process was determined to be of first-order reaction kinetics. Furthermore, a mechanism of this gelation process is also presented.